Disperse water-insoluble benzeneazo-3-acetyl-or 3-propionyl-aminodiphenyl-amine dyestuffs

ABSTRACT

DISPERSE WATER-INSOLUBLE AZO DYES IN WHICH A DIAZO COMPONENT, E.G. OF THE BENEZENE SERIES, IS COUPLED TO 3ACETYLAMINO OR 3-PROPIONYLAMINO-DIPHENYLAMINE AS THE COUPLING COMPONENT; THESE DYES WHEREIN THE NITROGEN ATOM OF THE DIPHENYLAMINE IS SUBSTITUTED BY METHYL, ETHYL, B-HYDROXY-ETHYL OR -PROPYL, B-HYDROXY-$-PROPYL, OR BACETOXY-ETHYL OR -PROPYL, WHEN USED ALONE OR IN MIXTURES WITH THE CORRESPONDING COMPOUNDS HAVING THE UNSUBSTITUTED NITROGEN ATOM ARE ESPECIALLY USEFUL FOR THE DISPERSION DYEING OF SYNTHETIC LINAR POLYESTER FIBROUS MATERIALS.

United States Patent Us (:1. 4 Claims ABSTRACTOF THE DISCLOSURE Dispersewater-insoluble azo dyes in which a diazo component, e.g. of the benzeneseries, is coupled to 3- acetylamino or 3-propionylamino-diphenylamineas the coupling component; these dyes wherein the nitrogen atom of thediphenylamine is substituted by methyl, ethyl, fl-hydroxy-ethyl or-propyl, fl-hydroxy-y-propyl, or flacetoxy-ethyl or '-propyl, when usedalone or in mixtures with'the corresponding compounds having theunsubstituted nitrogen atom are especially useful for the dispersiondyeing of synthetic linear polyester fibrous materials.

This invention relates to new and valuable azo dyes which are insolublein water and which have the general formula:

-OC-N in which:

D denotes the radical of adiazo component of the henzene, azobenzene,anthraquinone, thiadiazole or benzoisothiazole series;

R denotes a methyl, ethyl, fi-hydroxyethyl, ,B-hydroxypropyl,fl-hydroxy-y-chloropropyl, B-acetoxyethyl or pacetoxypropyl group;

R denotes a methyl or ethyl group;

X denotes a hydrogen, chlorine or bromine atom or a methyl, ethyl ormethoxy group; and

X denotes a hydrogen atom or a methyl group, and to mixtures of suchdyes with compounds having the I Formula I invwhic h R denotes ahydrogen atom.

D may be derived for example from:

4-nitr0aniline,

4-nitro-2-chloroaniline, I

4-hitro-2-brornoanilirie,

4'-nitro-2-methylaniline,

4-nitro-2-cyanoaniline,

4-nitro-2-cyano-6-chloroaniline,

4-nitro-2-methoxyaniline,

2,4-dinitroaniline,

2,4-dinitro-6-chloroaniline,

2,4-dinitro-6-bromoaniline,

2,6-dichloro-4-nitroaniline,

2,6-dibromo-4-nitroaniline,

Z-chloro-6-bromo-4-nitroaniline,

4nitro-2-cyano 6 bromoaniline,

2-methylsulfonyl-4nitroaniline,

2,4-dibro'mo-6-cyanoaniline or Z-cyano-s-methoxy-6-bromo-4-nitroaniline.

3,640,996 Patented Feb. 8, 1972 Aminoazobenzene and substitutionproducts derived therefrom, such as4-amino-Z-methyl-2',4'-dinitroazobenzene,4-amino-2',3-dichloro-4'-nitroazobenzene, 4-amino-3-chloro-2'-cyano-4'-nitroazobenzene or l-aminoanthraquinone are alsosuitable.

Examples of diazotizable heterocyclic amines of the thiadiazole orbenzoisothiazole series are:

2-a-rnino-5-phenylthiadiazole- 3,4) 2-amino-4-methylmercaptothiadiazole-2,4) 2-a(1;1i2; -4-/3-carbomethoxyethylmercaptothiadiazole-2-amino-4-,B-carboethoxyethylmercaptothiadiazole- (2,4) 3-amino-2,l-benzoisothiazole,

3-amino-5-nitro-2, l-benzoisothiazole,3-amino-5-nitro-7-bromo-2,l-benzoisothiazole or3amino-5,7-dibromo-2,l-benzoisothiazole.

Nitroanilines bearing chlorine, bromine and/or cyano as substituents andaminobenzoisothiazoles bearing nitro and/or bromine as substituents areof particular industrial importance.

Examples of radicals of the coupling components are:

3-acetylamino-N-methyldiphenylamine, 3-acetylamino-N-ethyldiphenylamine,3-acetylamino-N-fi-hydroxyethyldiphenylamine,3-acetylamino-N-18-hydroxypropyldiphenylamine,3-acetylamino-N-fi-acetoxyethyldiphenylamine,3-acetylamino-N-,Bacetoxypropyldiphenylamine, I3-acetylamino-N-B-acetoxyethyl-4'-acetylaminodiphenylamine,3-propionylamino-N-B-hydroxypropyldiphenylamine,3-propionylaminoN-B-hydroxyethyldiphenylamine,3-acetylamino-N-methyl-4-chlorodiphenylamine,3-acetylamino-N-fi-hydroxyethyl-4'-chlorodiphenylamine,3-acetylamino-N-fi-hydroxyethyl-4'-methyldiphenylamine,3-acetylamino-N-fl-hydroxyethyl-4'-methoxydiphenylamine,3-acetylamino-N-p-hydroxyethyl-2',4'-dimethy1diphenylamine,3-acetylamino-N-fi-hydroxypropyl-4'-methyldiphenylamine,3-acetylamino-N-B-hydroxypropyl-4-chlorodiphenylamine,3-acetylamino-N-{i-hydroxypropyl-4-acetylaminodiphenylamine,3-propionylamino-N-p-hydroxyethyl-4'-rnethoxydiphenylamine,3-propionylamino-N-p-hydroxyethyl-4'-methyldiphenylamrne,3-propionylamino-N-fi-hydroxyethyl-Z,4'-dimethyldiphenylamine,3-acetylamino-N-methyl-4'-methyldiphenylamine,3-acetylamino-N-fi-hydroxy-y-chloropropyldiphenylamine,3-acetylamino-N-fl-hydroxy-y-chloropropy1-4'-methyldiphenylamine,3-acetylamino-N-fi-hydroxy-v-chl0ropropyl-4'-chlorodiphenylamine,3-acetylamino-N-p-hydroxy-'y-chloropropyl-4'-acetylaminodiphenylamineand 3-acetylamino-N-B-hydroxyethyl-4-acetylaminodiphenylamine. I

Mixtures of a compound having the following Formula III and a compoundhaving the-following Formula IV bearing the same substituents areparticularly suitable mixtures of the compounds having the Formulae IIIand 3 Dyes which are of particular industrial value are those having thegeneral formula:

in which D denotes the radical of a chloro, bromo and/ or cyanosubstituted nitroaniline or the radical of a nitro and/or bromosubstituted benzoisothiazole and mixtures of such dyes with those havingthe general formula:

The new dyes may be obtained for example by reaction of a diazo compoundof an amine having the Formula II:

DNH (II) with a coupling component having the Formula III:

I} x Q-N- (III) 3 or with mixtures of compounds having the Formula IIIwith compounds having the Formula IV:

The new dyes are eminently suitable, especially in finely divided form,for dyeing structures such as fibers, filaments, threads, flock, wovenand knitted fabrics, particularly of polyesters, for examplepolyethylene terephthalate or polyesters based on terephthalic acid and1,4- dimethylolcyclohexane. Cellulose esters and polyamides may also bedyed with these dyes.

Particularly the mixtures of dyes according to this invention givebright dyeings of high tinctorial strength. Dyeing methods may includenot only high temperature dyeing and the thermosol method, but alsodyeing with carriers.

The invention is illustrated by the following examples, in which theparts and percentages are by weight.

EXAMPLE 1 6.05 parts of 2-chloro-4-m'troaniline is stirred with 32 partsof water and 32 parts of concentrated hydrochloric acid. One hour latera solution of sodium nitrite in 7 parts of water is added at from 0 to 5C. After another half an hour, the diazonium salt solution obtained isadded to a solution of 5 parts of 3-acetylamino-4'- chlorodiphenylamineand 6 parts of 3-acetylamino-4- chloro-N-(,B-hydroxyethyl)-diphenylaminein 100 parts of N-methylpyrrolidone and 150 parts of methyl alcohol.When coupling is over (after about on hour) the deposited dye is suctionfiltered, washed with water until neutral and dried. 14.5 parts of a dyemixture is obtained consisting of half each of the two compounds havingthe formula: V H

Red dyeings are obtained therewith on polyester fibers.

EXAMPLE 2 8.46 parts of 2-amino-3-bromo-5-nitrobenzonitrile is added inportions at from 0 to 5 C. to a mixture of 40 parts of sulfuric acid and11 parts of nitrosylsulfuric acid which contains 2.52 parts ,of sodiumnitrite. The whole is stirred for four hours at 0 to 5 C. The diazoniumsalt solution thus obtained is allowed to flow into a cooled solution of9.6 parts of 3-acetylamine-N- (fl-hydroxyethyl)-diphenylamine in partsof glacial acetic acid and parts of water. Another hour later, thedeposited dye is suction filtered, washed with water until it is neutraland dried. 9.5 parts of the compound having the formula:

2 CN EH2 I p -o I is obtained. It dyes polyester fibers bright blueshades having very good tinctorial properties.

EXAMPLE 3 8.46 parts of 2-'amino-3-bromo-5-nitrobenzonitrile isdiazotized as in Example 2. The resulting diazonium salt solution isdiluted at from 0 to 5 C. with 40 parts of glacial acetic acid and thenadded .to the cooled coupling solution. The coupling solution contains3.3 parts of 3-acetylaminodiphenylamine and 5.9 parts ofB-acetylamino-N-B-hydroxyethyldiphenylamine in 90 parts of methanol and90 parts of water. After all the diazonium salt solution has been added,the temperature is kept for half an hour at 0 to 5 C., the deposited dyeis suction filtered, washed until it is neutral and dried. 15 parts of adye mixture is obtained which consists of 40% of the compound having theformula:

' cool-t and 60% of the compound having the V Ho-pH CN I -q- -go-ro 6.83parts of 3-amino-5-nitro-2,l-benaoisothiazole is introduced in portionsat 10 to 15 C. into 27 parts of. concentrated sulfuric acid. As soon astheamine has dissolved, the whole is cooled to 5 C. and 35 parts-of amixture of glacial acetic acid and propionic acid 17:3)

f irt" is gradually added. Nitrosylsulfuric acid prepared from 2.52parts of sodium nitrite and 9 parts of concentrated sulfuric acid isthen added slowly at from to C. and the whole stirred for three hours atfrom 0 to 5 C. The diazonium salt solution is then added to a cooled 5solution of 2.8 parts of 3-acetylamino-4'-methyldiphenylamine and 6.5parts of 3-acetylamino-4-rnethy1-N- methyldiphenylamine in 50 parts ofN-methylpyrrolidone and 120 parts of methanol. The temperature is keptat 0 to 5 C. for half an hour, the deposited dye is suction filtered,washed with water until it is neutral and then dried. 11.5 parts of adye mixture consisting of of the compound having the formula:

60 parts of 85% phosphoric acid is added in the course C H gooe ocri 20and 70% of the compound having the formula is obtained. Blue dyeings areobtained therewith on polyester fibers or cloths.

EXAMPLE 5 of ninety minutes at 0 to 5 C. to a mixture of 10 parts ofconcentrated sulfuric acid and 10.5 parts of nitrosylsulfuric acid whichhas been prepared from 2.5 parts of sodium nitrite and 8 parts ofconcentrated sulfuric acid. Then, at from 0 to 5 C., 6.28 parts of 2-amino-5- phenylthiadiazole-(1,3,4) is introduced into this mixture Thetemperature is kept at from 0 to 5 C. for three hours and then thediazonium salt solution obtained is added to a cooled solution of 12parts of 3-acetamino-N- fi-hydroxyethyldiphenylamine in 100 parts ofN-methylpyrrolidone and parts of glacial acetic acid. The Whole isstirred for half an hour at from 0 to 5 C., parts of water and 40 partsof methyl alcohol are added and the deposited dye is suction filtered,washed and dried. l2

QR S 15 parts of the dye having the formula: 02M

t'zocrt is obtaine which dyes polyester cloth red violet shades.

The following table contains further examples using dyes having thegeneral formula:

in which D, R R, X and Y have the meanings given in the table in whichEx=Example No. and Color=Co1or of the dyeing on polyester Me=CH Et=C HTABLE Example D R R X Y Color 6 4-nitropheny1 Me 50% H, 50% 02H4OH 4-01H Red.

7.- 2-chloro-4-nitropheny1. Me 30% H, 70% C2H4OH 4-Me H Red.

8-- 2-methoxy-4-nitrophenyL- Me 30 H, 70% 02H 0H 4-Me H Red.

9.- 2-cyano-4-nitropheny Me H, 45% 02H4OH H H Violet.

10 Me 30% H, 70% 0-. H OH 4-OMe H Blue violet 11, Me 55% H, 45% C2H4OH4-Me H Violet.

. Me 40% H, 02H1OH 4-01 H Red violet 13 Me 60% H, 50% C2H4OH 4-Me HViolet.

14 Me 50% H, 50% CgHiOH 4-Me H Orange red.

15. 4-pheny1azophenyl Me 40% H, 60% 02H OH H H Red,

16- 2,6-dieh1oro-4-nitropl1eny1- Me 50% H, 50% OZH OH H H Ruby.

17. 2-chloro-6-bromo-4-nitrophenyl Me 40% H, 60% O2H OH 4-OMe H D0.

18. 2,6-dibromo-4-nitrophenyl- Me 50% H, 50% 02H4OH H H Red brown.

19. o Me 20% H, 80% CzHrOH 4-Me H Ruby.

20. ..do Me 50% H, 50% O2H4OH 4-Ol H Red brown.

21.. 2,4-dinitro43-brom0pheuyl. Me 50% H, 50% 0H4OH H H e.

22-- .-do Me 35% H, O2H OH 4-Me H D0. 28..2-eyano-6-bromo-4-nitropheny1. Me 20% H, 80% 0 11 0111 4-OMe H Do.

26... Me Me H H D0.

.do Me 50% H, 50% Me 4-Me H Do.

28. 2,4-dinitro-6-bromophenyl. Me 02H; H H H Blue violet. 29-2,6-dibrorno-4-nitrophenyl- Me C2H4OH H H Ruby.

32-- 2-methy1su1f0ne-4-nitropheny Me 60% H, 40% 0 H OH H H Bluish red.

33- fi-nitrobenzoisothiazolyl-(3) Me 02H4 H 4-Me H Blue.

'34-, 30% H, C2H4OH H H Do.

35.- 40% H, 60% CzH4OH 4-01 H Do.

36- 20% H, C H OH 4-OMe H Do.

37. 2H4OH 4-Me H Reddish blue. '38 50% H, 50% C2H4OH H H Blue.

39 40% H, 60% CzHiOH 4-Me H Do.

40- 50% H, 50% CzH4OH 401 H Do. '41- O2H4OH 4-Me H Blue green.

42. 50% H, 50% 02H OH 4-01 H Blue.

43. 40% H, 60% Me H H Do. 44. Benzoisothiazolyl-(S) 50% H, 50% Me H HDo. 2 45. 2-cyano-6-bromo-4-nltrophenyl. Me 40% H, 60% Et H H Do. 46-5-n1t1obenzoisothiazolyl-(3) Me 50% H, 50% E1; H H Do.

47-.. 2-eyano-6-bromo-4-nitropheny1 Me 40% H, 60% C2H4OH A-Me 2-Me Do.48-- 5-nitr0-7-bromobenzoisothiazo1y1-(3).. Me 40% H, 60% OZH4OH 4-V1e2-Me Blue green.

49 2-cyano-6-bromo-4-nitropheny1 Me 20% H, 80% CH: 4-Me H Blue.

CHOHMe 50 5-nitrobenzo1sothlazo1yl-(3) Me 20% H, 80% 0H2 4-Me H Do.

CHOHMe 51 2-cyano-6-bromo-4-nitropheny1 El; 60% H, 40% 02114011 4-Me2-Me TABLE.-'Continued I I Example D R R X Y Color;

52,, 2,4dinitro-fi bromophenyl Et 60% H, 40% 02H4OH 4Me 2-Me Blueviolet; 53 2-oyano-6-bromo-4-nitrophenyl. Et 50% H, 50% C H OH 4-Me HBlue, v 64. 2-chloro-4'nitrophenyl El; 30% H, 70% 02H OH 4-OMe H Redviolet; u 65.-. 2-cyano-0-br0mo-4-nitropheny Et 30 H, 70% CZH OH 4-OMe HBlue, 1

H I 1 Do.

011201 I 57 2-chlor-4-nitrophenyl Mo 40% H, 60% CHgCHOH 1'1 '11 D 2' 582-0yano-6-bromo-4-nitropl1cnyl Me 100%, 00% CHECHOH 4-Me H Do.

CHzCl I 59 5-nitrobenzoisothiazolyl (3) Mo H, 80% 011201101: 4 1x10 11Greenish 13m CHzOl 60 2-chloro4-nitrophenyl Mo 40% H, 60% C2H4O0OMe H HRed. 6L 2-cyanoJS-bromoA-nitrophenyl Me 40% H, 60% C H4OCOMe H H Blue.62. 5-nitrobenzoisothiazolyl-(3) Me 10% H, 90% C2H4OCOMe H H Do. 63.5-nitro-7-bromobenzoisothiazoly Me 10% H, 90% CzH4OCOMe H H Do, 64.5,7-dibromobenzoisothiazolyl-(3) Me C2IIOC0Me H H Do. 652-0yano-fi-bromo-i-nitrophenol Me H, 70% OI'IZCHOH H H Do.

66 do Me OHZ(IJHOH 4-01 H Do,

67 5-nitr0benzolsothiaz0lyl-(3) Me 10% H, 90% CHzCHOH 4-01 H Do.

CHzCl 68 5-nitro-7-bromobenzoisothiazolyl-(Ii) Me 10% H, 90% CHzCHOH4-01 H Do.

69 2'cyano-6-bromo-4-nitrophenyl Me 30% H, 70% CH2OHOH 4-01 H J Do.

CHzCl 70 E-nitrobenzoisothiazolyl-(3) Me 00% H, CHzCHOH 4-01 H Do.

I CHzCl 71 5-njtro-7-bromobenzoisothiazolyl-(3) Me H, 50% CHZQHOH 4-01 HDo.

72 l-anthraquinonyl Me 40% H, 60% 02H40H H H. Redbrown.

We claim: 4. A dye as claimed in claim 1 of the'formula 1. A dye havingthe formula THICHzOH 02 N=N I N 0: NH 0 0 CH 1 4 NHcoR References Citedin which: 50 UNITED STATES PATENTS Z denotes hydrogen, chlorine,bromine, cyano or nitro; 2,083,308 6/1937 Senn -5; 260207.1 X Z denoteshydrogen, chlorine or bromine; 2,289,349 7/1942 Dickey et al. 260-207.1X R denotes methyl, ethyl, ,B-hydroxyethyl, fi-hydroxy- 2,683,709 7/1954 Dickey et al. 260-158 propyl, fl-hydroxy-'y-chloropropyl,,B-acetoxy- 2,730,523 1/ 1956 Dickey et a1. 260158 ethyl orfi-acetoxypropyl; 2,857,371 10/ 1958 Staley et a1. 260158 X R denotesmethyl or ethyl; 2,889,315 6/1959 Bossard et al. 260-158 X X denoteshydrogen, chlorine, bromine, methyl, ethyl or 3,438,963 4/1969 Robbinsmethoxy; and 3,455,898 7/ 1969 Y denotes hydrogen or methyl.

Seefelder et al. 260---158 2. A dye as claimed in claim 1 in admixturewith the FLOYD HIGEL,P1'ima1'Y Examiner same compound of the Formula Ibut in which R is hydrogen.

3. A dye as claimed in claim 1 wherein R is ,B-hydroxyethyl, R is methyland X and Y each represent hydrogen.

US. Cl. X.R.

8-4, 41 R, 41 B, 41 C, 50; 117-138.8 R, 138.8 F, 144; 260-37 N, 40 R,158, 187, 192, 207

